Aminoalkylaminonaphthalene sulphonic acids



26 or naphthylamines the corresponding a 55 form to -aminoalkyl u.

Patented do 9 5250 UNITED STATES PATENT OFFICE.

JOHANN HUISMANN, OF WIESDORI, NEAR COLOGNE, WALTER DUISBERG, O1 LEVER- KUSEN, NEAR OOLOGNE, AND WINFRIED HENTRICH AND LUDWIG ZEH, O1 WIRE- DORF, NEAR COLOGNE, GERMANY, ASSIGNORS TO GRABSELLI nm'rurr COR PORATION, OF- NEW YORK, N. Y., A CORPORATION OF DELAWARE.

AIINOALKYLAIINONAPHTHALENE SULPHONIC ACIDS.

1T0 Drawing.

To all whom it may concern:

Be it known that we, (1) JOHANN Hurs- MANN, (2) WALTER Dmsanne, (3) WI1 FRIED HENTRICH, and (4) LUDWIG Zen, citi- 5 sons of Germany, residing at (1) Wiesdorf,

aminonaphthalene Sulphonic Acids, of which the following is a s cification.

our invention resides in a process of producin o -aminoal l-substituted aminonapht alene sulphonic acids and in the compounds themselves, which are valuable dyestufi intermediates.

It is well known that by reacting with primary or secondar amines in presence of alkali metal bisu tes upon naphillglls In the foregoing formulae the sulphonic ral duction of our amino-alkylamino-na hthaacid group may occupy any of the save possible positions in the naphthalene nudone: as indicated. Both 1; of naphthalene sulphonic acids, that is, ose having the reactive roup in the alpha position and those having the reactive group in'the beta position react with aliphatic diamines m,

the same way, corresponding naphthol sulphonic acids and naphthylamine sulphonic acids giving the same end product.

In addition to the straight naphthol and naphthylamine sulphonic acids, aminonaph-l thol, dihydroxy-naphthaleneas well as naphthylene-diamin-sulphonic acids Application ma Iaroh a, 1925. Serial no. 1:,c1o.

naphthylamines areobtained. If aliphatic diamines such as ethylenediamine, or its homologues are allowed to react withthe naphthols both amino groups are liable to be substituted and mixtures of i. e. aminoethylamidonaphthalene, ethylenedinaphthylamines and eventually higher alkylated products are obtained.

We have now found that if aliphatic diamines are allowed to reactin presence of soluble salts of sulfurous acid upon naphthalene sulphonic. acids having one of the reactive groups, amino and h droxyl, only one of the amide groups is so tituted by a naphthalene nucleus, and m -aminoalkylaminonaphthalene sulphonic acids are obtained with excellent yields.

The reaction proceedsmost likely in the following way The diamines which we use for the prothe following examples in which the parts given are by weight Example 1.246 parts of lna hthol-4- sulphonate of soda are suspends in 880 parts of a sodium bisulfite solution to which 450 parts of a 20% aqueous solution of ethylene-diamine are added and the mixture is boiled at reflux with ood stirrin The naphthol sulphonic acid issolves grad ually. At the same time the 1- (aminoet yl)- amino-naphthalene-4-sulphonic acid se arates. The reaction is carried out at boiling temperature for several hours. The mixture is then cooled and filtered, on a vacuum filter. The mother liquor is practically free from raw material and from the desired end product. The separated product is sludged with water and boiled with h drochloric acid in order to expel all the sulp urous acid from the bisulfite. By cooling, the aminoethyl-na hthionic acid scparatesand is filtered oil? It is a light greyish powder very diflicultly soluble even in hot water. I It forms a sodium salt which is soluble to a certain extent in hot water but also difiicultly soluble in cold water. Sus nded in water and treated with sodium nltrite and hydrochloric acid a nitroso} compound is quantitatively formed which nitroso compound is a crystalline yellowish colored powder relatively soluble in water.

Exwmplc 2.246 parts of 2-naphthylamine-7-sulphonate of soda are suspended in 1750 parts of a 40% sodium bisulfite solution to which 900 parts of a 20% aqueous solution of eth lenediamine are added and the mixture is iled at reflux for 12hours .while stirring. The napthylamine sulphonic acid disolves gradually and then the 2 (aminoethyl) aminonaphthalene 7 sulphonic acid starts :to separate. After coolmg, the crystalline product is filtered ofi, sludged with hydrochloric acid to Congo acid reaction and boiled to expel the sulfurous acid. After cooling, the pure 2- (aminoethyl) -alminonaphthalene-7-sulphonic acid is filtered oil and dried. It is a white powder practically insoluble in cold and hot water,

the sodium salt is slihtly soluble in hot water and very diflicifltly soluble in cold water. The nitroso compound is obtained by dissolving the sodium salt in hot water, adding the molecular equivalent of sodium nitrite and pouring the solution into ice cold diluted hydrochloric acid. The nitroso compound separates as beautiful orange colored crystals quite insoluble in cold water and soluble in hot water from which it can be re-crystallized.

Exam Ze 3.-261 parts of 2-amido-8- naphtho -6-sulphona te of soda are suspended in. 1750 parts of a 40% sodium bisulfite solution to which 300 parts of a 20% aqueous solution of eth lenediamine are added. The mixture is bolled at reflux for 12 hours,

nuance cooled, filtered oil and the paste suspended in enough hydrochloric acid to secure Congo acid reaction at the end and, b boiling, all the sulfurous acid is expel ed. The 2- (aminoethyl) amino-8-naphthol-6-sulphonic acid is obtained with an excellent yield. It is a white powder diflicultly soluble in water but quite soluble in hot diluted hydrochloric acid. With nitrous acid it forms a brownish crystalline nitroso compound.

Ewwmple 4.364 parts 2.8-dihydr0xynaphthalene-3.6-disulphonate of soda are suspended in 880 parts of a 40% sodium bisu to solution and 300 parts of a 20% aqueous solution of ethylenediamine and the mixture is-boiled at reflux for hours. The solution is then diluted with its volume of water and boiled with an excess of hydrochloric acid. After cooling the 2-(aminoethyl) -amino -8- hydroxynaphthalene-3.6-disulphonic acid is filtered ofl. It contains traces of unconverted 2.8-dihydroxynaphthalene-3.6-disulphonic acid and ethylene- 2.2-diamino8.8 -dihydroxydinaphthy -3.3- 6.6'-tetrasulphonic acid. t is purified b recrystallization from hot water to whic sodium acetate has been added. It is a whitish powder easily soluble in hot water.

Example 5.246 parts 2-naphth lamine- 7-sulphonate of soda are dissolv in 500 parts water and 880 arts of a 40% sodium isulfite solution ad ed. To this is added a solution of 241 parts normal butylenediamine-dichlorhydrate in 500 parts water and-.the mass heatedat -95 for about 16, hours. The o-amino-butylr2-naphthylamine-'Z-sul honic acid se arates as white floccules. r coolin e reaction product is filtered, the sulp onic acid dissolved in water and boiled with an excess of hydrochloric acid to .expel the sulfurous acid.

The solution is then made slighltly alkaline by the addition of soda ash. e difiicultly soluble sodium salt of the m-aminobutyl-2- naphthylamine-7-sulphonate of soda separates is filtered oil and dried. It is a white powder easily soluble in dilute hydrochloric acid; with sodium nitrite in acld solution it forms a crystalline light yellow colored nitroso compound.

We claim '1. The process of producing m-aminoalkylamino-naphthalene sulphomc acids which consists in reacting wit aliphatic diamines in (presence of soluble salts of sulfurous aci upon naphthalene sulphonic acids having at least one of the reactive groups amino and hydro l.

2. The processo producing m-aminoalkylamino-naphthalene sulphonlc acids which consists in reacting in presence of soluble salts of sulfurous acid with ali haticdiamines upon naphthylamine sulp onic acids.

=3. The process of producing co-aminoethylamino-naphthalene sulphomc acids which III nuance consists in reactin with eth lene-diamine in presence of solub e salts 0 sulfurous acid upon naphthalene sulphonic acids having at least one of the reactive groups amino and h droxyl.

4. e process of producing m-aminoeLhylamino-naphthalene sulphonic acids, which consists in reactin with ethylenediamine in furous aci upon naphthylamine sulphonic acids. v

5. As new products the w-aminoalkylaminonaphthalene sulphonic acids which can be obtained by acting with ali hatic diamines in resence of soluble sa ts of sulfurous aci 5 upon naphthalene sulphonic acids having at least one of the reactive groups amino and hydroxyl, which maminoalkylamino naphthalene sulphonic acids are whitish powders generally diflicultly soluble in water, form alkali metal resence of souble salts of sulsalts, are soluble in dilute mineral acids and form characteristic, crystalline and colored nitroso compounds.

' 6. As new products the m-aminoethylaminonaphthalene sulphonic acids which can be obtained by reacting with ethylene'diamine in presence of soluble salts of sulfurous acid upon naphthalene sulphonic acids having at least one of the reactive groups amino and hydroxyl, which m-aminoethylamino-naphthalene sulphonic acids are white powders, generally difiicultly soluble in water and orm alkali metal salts, soluble in dilute mineral acids and characteristic, colored-and c stalline nitroso compounds.

11 testimony whereof we have hereunto set our hands.

J OHANITHUISMANN. WALTER DUISBERG. WINFRIED HENTRICH. LUDWIG ZEH. 

